Physical properties of the spin-crossover compound hexakis(1-methyltetrazole- N4)iron(II) triflate, steady state and relaxation studies, X-ray structure of the isomorphic Ni(II) compound

Abstract

The synthesis and characterization of the spin transition compound hexakis(1-methyltetrazole- N 4)iron(II) trifluoromethanesulfonate obtained from the reaction of 1-methyltetrazole and iron(II) triflate are described. The spin transition of [Fe(mtz) 6](CF 3SO 3) 2 ( 1) presents a hysteresis loop in magnetism with T ↓=157.0 and T ↑=179.5 K. Only one-third of the Fe(II) ions undergo this transition, the other two-thirds of the ions remain in the high-spin state. Mössbauer spectroscopy and relaxation studies have shown that the actual width of the hysteresis is only 12 K, with T ↓=167.5 and T ↑=179.5 K. Thermal spin-state trapping appears to be possible. The trapped high-spin state is stable up to 103 K. The relaxation is not first-order. After irradiation with red light, reverse light-induced excited spin state trapping (LIESST) is observed. The new low-spin state is stable up to 42 K. Also, its relaxation to HS is non-first-order. A reverse light-induced thermal hysteresis loop of approximately 7 K width is present too. No LIESST effect could be observed. Finally, a ferromagnetic type of coupling has been recognized, which is temperature and field dependent.